Certain non-terpenoid juvenile hormone mimicking compounds and their use in controlling insects

ABSTRACT

Compounds having the formula   in which R is alkyl having 1 to 8 carbon atoms, R1 is hydrogen or alkyl having 1 to 4 carbon atoms, R2 is hydrogen or alkyl having 1 to 4 carbon atoms, R3 is alkyl having 1 to 8 carbon atoms, X is oxygen or sulfur and X1 is oxygen or sulfur are useful to control insects.

United States Patent Pallos Nov. 4, 1975 CERTAIN NON-TERPENOID JUVENILE HORMONE MIMICKING COMPOUNDS AND THEIR USE IN CONTROLLING INSECTS [75] Inventor: Ferenc Marcus Pallos, Walnut Creek, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: July 25, 1974 [211 App]. No.: 491,919

Related US. Application Data [62] Division of Ser. No. 257,092, May 26, 1972, Pat. No.

[52] US. Cl. 424/300; 424/D1G. 12 [51] Int. Cl. AOIN 9/12; AOlN 9/20 [58] Field of Search 424/300, DIG. 12;

OTHER PUBLICATIONS Borkovec, A., Insect Chemosterilants, Vol. V11 (1966) pp. 61-63.

United Kingdom 260/455 A Germany 260/455 A Primary Examiner-V. D. Turner Attorney, Agent, or FirmEdwin H. Baker [57] ABSTRACT Compounds having the formula in which R is .alkyl having 1 to 8 carbon atoms, R is hydrogen or alkyl 'having 1 to 4 carbon atoms, R is hydrogen or alky1-, having l to 4 Carbon atoms, R is alkyl having 1 to Scarbon atoms, X is oxygen or sulfur and X is oxygen or sulfur are useful to control insects.

9 Claims, No Drawings CERTAIN NON-TERPENOID JUVENILE O v V j p O HORMONE MIMICKING COMPOUNDS AND H i l l H I NaH/H O THEIR USE IN CONTROLLING INSECTS g l |,T

' 5 ll f This is a division of application Ser. No. 257,092, R x C lLCHCHhL Cx'-fw filed May 26, 1972, now U.S. Pat. No. 3,846,466. n

This invention relates to the use of certain novel preferably the reaction is carried out in a solvent chemical compounds effective in combatting noxious such as water, with stirring by slowly adding the alkyl insects, more particularly, the chemical compounds are chloro(thio)formate or mixture of alkylchloro(thio)- certain 1,2 bis [alkyl (thio) carbamoyl] ethanes, formates to the diamirie in the presenceof an acid ac- A new class of selective compounds has been found ceptor, such as a solution of NaOH, at a temperature which exerts a disrupting influence upon the normal around 0C. followed by stirring at room temperature development of insects. Such compounds impede the to complete the. exothermic reaction. The reaction metamorphosis of larvae to pupae and pupae to adults product is recovered by conventional techniques'such resulting in the formation of abnormal members-of the as extracting with methylene chloride, washing the soltreated species which may also be non-viable orste'rile. vent phase with water, followed by drying with anhy- This ultimately leads, indirectly at least, to the destrucdrous MgSO Finally, the solvent is filtered and retion of a pest population. moved by vacuum stripping.

The compounds of the present invention are believed Preferably, the reaction is carried out using equal to have the further advantages that they are non-toxic mole amounts of the reactants, although a slight excess to warm blooded animals and are highly effective in of a reactant can be used. V controlling insects at low dosages. In compounds where Ii and R are different and/or X One embodiment of the present invention is conand 'X-: are different'then a mixture of desired comcerned with novel pesticidal compositions. pounds result=which can be separated byuconventional In another embodiment, the invention is concerned techniques. I with the active pesticidal component of such composi- Preparation of-thecompounds'ofthis invention-is iltions. lustrated by the following specific-examples.

In still another embodiment, the invention is conv t. cerned with a process for controlling insects by hinder- EXAMPLE I ing or impeding the metamorphosis and reproduction N',N'-diethyl-I,2-bis(n-propylthiocarbamoyl) ethane ofthe insects. i-

The compounds of the present invention that are use- {2H5 :1 i ful in controlling insects are those havingthe formula x v g amine, 25 milliliters water, 4.Q;grams -5f) percent) in which R is alkyl having 1 and 8 carbon atoms, prefer- 40 9 solut'loh-(o-osllholel E i hhxed. hf, f fla ably .2 to 6 carbon atoms; R is hydrogen or alkyl having equlpped l 'f 9 at-W9 l h i 5h I to 4 carbon atoms, preferably hydrogen; R is hydrom J -an a -9. s ,m$ genor, preferably,.alkyl having 1 to 4.carbon atoms, 'P f h' hla f Y Y P Ed h h preferably 1 to 3 carbon atoms; R is'alkyl having I to m'xmre causmg a h l' h f hh h T l i h 8 carbon-atoms, preferably 2 to 6 carbon atomsyX is remove-Cl h the mlxtuhe Shirred- F 9 oxygen or sulfur and X is oxygen or sulfur. temperature hh hi hh h P u recov' As indicated heretofore, theabove compounds are ered y extracting with I00 milliliters CH Cl2 and F l useful in impeding the metamorphosis and/or the ref It Wlth 75 hl hh i l' followed by TY B production of insects. The activity of the compounds is h Mgso4' The organ": h filtered g h h such that insects at any stage of their development can to weld grams of h desh'ed Pmduct- ND be effective, treated therewith LR. and n.m.r. analysis confirm the structure.

The compounds of this invention can be prepared by The followlhg a table of celtam Selected the following reaction. pounds that are preparable according to the procedures described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the specification.

TABLE I 0 R R 0 w R x c -i 1cH,cH,N cgx R= Compound Number. X R' R2 3 X R ND 1'' nC=H, s C,H, cat, s nC,H-, l.436I 2 n.C -,H 'S nC,H-, nC;,I-I s nC,H-, 1.5000 3 C,H, s C H H s c H, 1.5235 4 n C,.H s H C,H s n C,H, 1.5110 5 i-C H s cm, 0,5, s i-C,I-I-, 6 CH: 5 C2H.5 z s S a 7 n-(:,H. s cm, C,H, s n-cJ-l, [.4980 -a i-c,i-l, s :,,H QR, S i-CJI, 1.5964

"=Prepared in Example I.

The degree of activity of a candidate compound to hinder or impede the metamorphosis ofinsects is measured by treating the penultimate larval stage of a representative insect with the compound and examining it after its last molt toward the adult form for retention of immature features.

Specifically, yellow mealworm, Tenebrio molitor, I..., larvae are maintained at 28C. and 40 percent humidity on a diet of bran flakes. Prepupae are collected from the culture and kept in separate containers. The pupae collected once daily, are 1-25 hours old at the time of treatment. By means of a syringe, suitable amounts of candidate compounds in 0.5 or 1.0 iLl of acetone are applied to the venter of Tenebrio molitar, L. pupae. Treated pupae are maintained at 28C. and 40 percent humidity until the adults emerged.(usually within 6-8 days). Emerged adults are graded as positive, negative,

or dead. To be considered a positive response, the presence of typical pupal cuticle, urogomphi, gin trap, and abnormal wings, etc., are required. For each test, '1 group of 10 pupae was used.

The dose of a candidate compound per pupa that is needed to give a positive response in the above insecticidal evaluation test for 5 of the 10 pupae is determined. Table ll shows these doses under the column ED the ED being an abbreviation for effective Z-methylbutyl TABLE ll-continued Compound Number ED A s/p p The compounds of this invention. are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, d us-ts, and aerosol sprays. in general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc., water; emulsifying agents; surface active agents; talc; pyrophyllite; diatom-ite; gypsum; clays; propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc., upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile.

The compounds can also be combined with baits in a conventional manner.

The precise manner in which the pesticide compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition, for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 50 percent by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or Ci R R-X-C-IL in which R is alkyl having 2 to 6 carbon atoms; R is hydrogen or alkyl having I to 4 carbon atoms; R is alkyl having 1 to 4 carbon atoms; R is alkyl having 2 to 6 carbon atoms; X is sulfur and X is sulfur.

2. The method of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R is hydrogen. R is alkyl having 1 to 3 carbon atoms, R is alkyl having 2 to 6 carbon atoms, X is sulfur and X is sulfur.

3. The method of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R is alkyl having 1 to 3 carbon 6 atoms, R 's alkyl having l to 3 carbon atoms, R is alkyl having 2 to 6 carbon atoms, X is sulfur and X is sulfur.

4. The method of claim 1 in which R is isobutyl, R is hydrogen, R is ethyl. R is isobutyl, X is sulfur and X is sulfur.

5. The method of claim 1 in which R is secondary butyl, R is hydrogen, R is ethyl, R is secondary butyl, X is sulfur and X is sulfur.

6. The method of claim 1 in which R is n-propyl, R is hydrogen, R is ethyl, R is n-propyl, X is sulfur and X is sulfur.

7. The method of claim 1 in which R is isobutyl, R is ethyl, R is ethyl, R is isobutyl, X is sulfur and X is sulfur.

8. The method of claim 1 in which R is isobutyl, R is methyl, R is ethyl, R is isobutyl, X is sulfur and X is sulfur.

9. The method of claim 1 in which R is Z-methylbutyl, R is hydrogen. R is ethyl, R is 2-methylbutyl, X is sulfur and X is sulfur. 

1. A METHOD OF IMPEDING THE METAMORPHASIS OF TENEBRIO MOLITOR COMPRISING APPLYING THERETO AT ANY STAGE OF ITS DEVELOPMENT A METAMORPHASIS INHIBITING AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R1 is hydrogen, R2 is alkyl having 1 to 3 carbon atoms, R3 is alkyl having 2 to 6 carbon atoms, X is sulfur and X1 is sulfur.
 3. The method of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R1 is alkyl having 1 to 3 carbon atoms, R2 is alkyl having 1 to 3 carbon atoms, R3 is alkyl having 2 to 6 carbon atoms, X is sulfur and X1 is sulfur.
 4. The method of claim 1 in which R is isobutyl, R1 is hydrogen, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 5. The method of claim 1 in which R is secondary butyl, R1 is hydrogen, R2 is ethyl, R3 is secondary butyl, X is sulfur and X1 is sulfur.
 6. The method of claim 1 in which R is n-propyl, R1 is hydrogen, R2 is ethyl, R3 is n-propyl, X is sulfur and X1 is sulfur.
 7. The method of claim 1 in which R is isobutyl, R1 is ethyl, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 8. The method of claim 1 in which R is isobutyl, R1 is methyl, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 9. The method of claim 1 in which R is 2-methylbutyl, R1 is hydrogen, R2 is ethyl, R3 is 2-methylbutyl, X is sulfur and X1 is sulfur. 